CN112409693B - Halogen-free flame retardant with good flame retardance and processability and flame-retardant resin composition - Google Patents
Halogen-free flame retardant with good flame retardance and processability and flame-retardant resin composition Download PDFInfo
- Publication number
- CN112409693B CN112409693B CN202011350705.8A CN202011350705A CN112409693B CN 112409693 B CN112409693 B CN 112409693B CN 202011350705 A CN202011350705 A CN 202011350705A CN 112409693 B CN112409693 B CN 112409693B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- flame
- halogen
- retardant
- processability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The halogen-free flame retardant with good flame retardance and processability and the flame-retardant resin composition are composed of piperazine phosphate, melamine and derivatives thereof, metal salt flame retardant synergists, hyperdispersants, low-melting-point lubricating flame retardant aids and organic sulfur-containing compounds. The flame-retardant resin composition consists of a halogen-free flame retardant with good flame retardance and processability and resin, wherein the mass percentage of the halogen-free flame retardant with good flame retardance and processability is 15-50%. The halogen-free flame retardant disclosed by the invention has excellent flame retardant property, better compatibility and dispersibility in resin, smooth surface of a flame-retardant finished piece, no white spots and high yield.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a halogen-free flame retardant with good flame retardance and processability and a flame-retardant resin composition.
Background
In halogen-free flame retardant research and polymer material product development, piperazine phosphate flame retardant shows high-efficiency flame retardant performance, wherein piperazine pyrophosphate has higher thermal stability and char formation performance, and has been widely applied to halogen-free flame retardant materials of polypropylene and glass fiber reinforced systems. In 1986, U.S. patent No. 4599375 discloses a flame retardant synthetic resin composition comprising (a) a synthetic resin, (b) piperazine pyrophosphate, (c) a melamine pyrophosphate salt, and (d) titanium dioxide or silicon dioxide. The use of piperazine pyrophosphate as a halogen-free flame retardant in polypropylene is disclosed in many patents such as CN101827885A, CN109503941A, CN104119610A, CN105061887 a. CN105694443B discloses the flame retardant property of piperazine pyrophosphate and hypophosphite compound flame retardant in glass fiber reinforced nylon materials. By adopting the conventional flame retardant system, although the flame retardant performance of the material can be improved, the piperazine pyrophosphate flame retardant is used as a strong polar compound, powder is easy to absorb water and agglomerate, so that bridging and strip breakage are easy to occur in the processing process, and the production efficiency is reduced. Meanwhile, because the compatibility of the powder and the resin is poor, the powder and the resin are unevenly dispersed in the melting process of the resin, so that the surface of a spline is rough and has white spots, and the mechanical property of the material is seriously affected. In some low-melt-index polypropylene and glass fiber reinforced systems, the melt index of the resin is obviously reduced due to the addition of the flame retardant powder, the processing fluidity is poor, the requirement on an injection molding process is increased, and the yield is low. Therefore, the inhibition of secondary agglomeration of piperazine phosphate, especially piperazine pyrophosphate powder, to improve the dispersibility and compatibility in the resin and reduce the influence of the flame retardant on the fluidity of the resin melt becomes a problem to be solved in order to further expand the application field of piperazine pyrophosphate flame retardant systems.
In patent CN1922260B, silicone oil is used to treat piperazine pyrophosphate flame retardant to inhibit agglomeration of powder, so as to improve the powder characteristics. CN110483898A discloses that a lubricant and silicone oils are used in combination to treat piperazine pyrophosphate. The silicone oil treatment method improves the problem of moisture absorption and agglomeration of piperazine pyrophosphate, has good water resistance in normal temperature environment, but the silicone oil has low melting point, is easy to soften again after being heated, so that the water resistance of the modified product in high temperature, high humidity and hot water environment is poor, and the powder is easy to agglomerate after long-term storage without isolation and dispersion treatment after silicone oil coating treatment. Patent CN111032829a adopts alumina monohydrate to improve the processing formability and anti-dripping, but the compatibility of inorganic powder and resin is poor, deteriorating the mechanical properties of the material. Patent CN110079009a discloses that hyperdispersant, high length-diameter ratio filler and nano filler are used in a piperazine pyrophosphate flame retardant system to obtain a halogen-free flame retardant polypropylene material with ultrahigh fluidity, but a double screw extruder with a second-order side feeding port is used in processing, so that the requirement on processing equipment is high. According to the related documents and patent descriptions, it is completely impossible to speculate that the following flame retardants can be obtained: the piperazine phosphate compound flame retardant is mixed with the hyperdispersant, the low-melting-point lubricating flame retardant and the organic sulfur-containing compound to inhibit secondary agglomeration of flame retardant powder, improve the dispersibility and compatibility of the flame retardant in the resin, ensure no dripping during combustion, improve the melt index of the flame retardant resin, simultaneously ensure that the surface of a product is smooth, and endow the resin with better flame retardant property and processability.
Disclosure of Invention
In view of the above, the present invention aims to provide a halogen-free flame retardant and a flame retardant resin composition having good flame retardance and processability, and in particular to a halogen-free flame retardant and a resin composition having good flame retardance and processability, which are obtained by adding a hyper-dispersant, a low-melting lubricating flame retardant auxiliary agent and an organic sulfur compound to a piperazine phosphate compound flame retardant, and which have less secondary agglomeration, good powder flowability, good compatibility and dispersibility in resins, no dripping during combustion, and good flame retardance and processability, so as to solve the above problems.
The halogen-free flame retardant with good flame retardance and processability consists of piperazine phosphate, melamine and derivatives thereof, a metal salt flame retardant synergist, a hyperdispersant, a low-melting-point lubricating flame retardant auxiliary agent and an organic sulfur-containing compound. The low-melting-point lubricating flame-retardant additive comprises, by mass, 40-80% of piperazine phosphate, 20-50% of melamine and derivatives thereof, 1-10% of metal salt flame-retardant synergist, 0.01-5% of hyperdispersant, 0.01-10% of low-melting-point lubricating flame-retardant additive and 0.01-5% of organic sulfur-containing compound, wherein the low-melting-point lubricating flame-retardant additive is liquid organic phosphate or solid with the melting point lower than 200 ℃ in a conventional state.
Further, the piperazine phosphate is one or a mixture of more of piperazine monophosphate, piperazine diphosphate, piperazine pyrophosphate and piperazine polyphosphate which are not subjected to surface treatment or are subjected to surface treatment modification.
Further, the melamine and the derivative thereof are one or a mixture of more of melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate and melamine cyanurate.
Further, the metal salt flame retardant synergist is one or a mixture of more of zinc oxide, zinc borate, silicon dioxide, titanium dioxide, aluminum oxide, aluminum hypophosphite, diethyl aluminum hypophosphite, dimethyl aluminum hypophosphite, diphenyl aluminum hypophosphite, magnesium silicate, aluminosilicate, zinc hypophosphite, zinc stannate, zinc sulfide, dimethyl zinc hypophosphite, diethyl zinc hypophosphite and diphenyl zinc hypophosphite.
Further, the hyperdispersant is one or a mixture of a plurality of polyether hyperdispersant, polyester hyperdispersant and polyacrylate hyperdispersant.
Further, the low-melting-point lubricating flame retardant auxiliary is one or a mixture of (6H) -dibenzo- (c, e) (1, 2) -phosphinohexane-6-one (DOPO), [ (6-oxo- (6H) -dibenzo- (c, e) (1, 2) -phosphinohexane-6-one) methyl ] -succinic acid (DOPO-I TA), 10- (1, 4-butanedioic acid-2-yl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-1-oxide (DOPO-MA), 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10- hetero phenanthrene-10-oxide (ODOPB) and/or hexaphenoxy cyclotriphosphazene, o-phenylenediamine cyclotriphosphazene and/or tert-butyl triphenyl phosphate, tetraphenyl bisphenol A diphosphate, tetraphenyl resorcinol diphosphate, phenyl phosphate and/or tris (epoxypropyl) isocyanurate in organic heterocyclic compound hexa-phosphazene.
Further, the organic sulfur-containing compound is selected from one or a mixture of more of n-dodecyl sulfide, 4 '-dihydroxydiphenyl sulfide, 4' -sulfonyl diphenol, alkyl phenol disulfide, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and diphenyl sulfone.
The flame-retardant resin composition consists of the halogen-free flame retardant with good flame retardance and processability and resin, wherein the mass percentage of the halogen-free flame retardant with good flame retardance and processability is 15-50%. The halogen-free flame retardant and the resin are granulated by a double screw extruder to prepare the flame retardant resin composition, and the temperature of the extruder is 180-280 ℃.
Compared with the prior art, the halogen-free flame retardant provided by the invention consists of piperazine phosphate, melamine and derivatives thereof, metal salt flame retardant synergist, hyperdispersant, low-melting-point lubricating flame retardant auxiliary agent and organic sulfur-containing compound, wherein different elements play different roles in the flame retardant, specifically, the piperazine phosphate compounded halogen-free flame retardant plays a flame retardant role mainly through condensed phases, and acid source, carbon source and air source cooperate, so that an expanded carbon layer is formed on the surface of the material for heat insulation, oxygen isolation and heat transfer, and further combustion is interrupted. After the low-melting-point lubricating flame-retardant auxiliary agent is added, the melt index of the resin can be increased, the compatibility and the dispersibility of the flame retardant are improved, and the processing efficiency is improved, but the melt dripping is promoted during combustion, and the auxiliary agent with the anti-dripping effect is required to be matched. The organic sulfur-containing compound is used as a supplementary acid source, sulfur element can change the decomposition process of the polymer, and has better flame-retardant synergistic effect with phosphorus and nitrogen elements in flame retardant, phosphate, DOPO, phosphazene and other lubricating processing aids, sulfuric acid substances are released by thermal decomposition during combustion, and the generated acid and carbon source are combined to generate esterification reaction, so that the flame retardance of condensed phases is promoted to form carbon, the quality and the continuity of a carbon layer are improved, and secondary combustion caused by molten drops is prevented. Meanwhile, the organic sulfur-containing compound has good compatibility with the resin material, and the influence of the halogen-free flame retardant on the mechanical property of the material is reduced. Meanwhile, the invention has the following advantages:
(1) Aiming at the problems that piperazine phosphate compound flame retardant is easy to absorb moisture and agglomerate and is easy to process and bridge, hyper-dispersants with similar polarities are selected to isolate flame retardant powder, so that secondary agglomeration of the powder is effectively inhibited, and the powder characteristics and the dispersibility in resin are improved.
(2) Liquid phosphate or DOPO, phosphazene derivatives and other low-melting-point auxiliary agents with certain flame retardant function are added, and the liquid phosphate or DOPO, phosphazene derivatives and other low-melting-point auxiliary agents can be quickly melted in the processing process, so that the melt flow rate of the flame retardant resin composition can be increased, the shearing force and the processing resistance of a screw are further reduced, the degradation of the flame retardant due to shearing heat is avoided, the processing tolerance and the production efficiency are improved, and meanwhile, the dispersibility and the compatibility of the flame retardant powder in the resin are improved.
(3) The organic sulfur-containing compound is used as a supplementary acid source, so that the condensed phase can be promoted to form carbon, the quality and the continuity of an expanded carbon layer are improved, and further, combustion molten drops can be effectively inhibited, and the secondary ignition of a fire disaster is prevented.
(4) The flame retardant disclosed by the invention has higher thermal decomposition temperature, is suitable for systems with higher processing temperatures such as continuous long glass fiber reinforced polypropylene and the like and injection molding processes, and has the advantages of smooth surface of a flame retardant finished piece, no white spots and high yield.
Detailed Description
Specific embodiments of the present invention are described in further detail below. It should be understood that the description herein of the embodiments of the invention is not intended to limit the scope of the invention.
The halogen-free flame retardant with good flame retardance and processability comprises, by mass, 40-80% of piperazine phosphate, 20-50% of melamine and derivatives thereof, 1-10% of metal salt flame retardant synergist, 0.01-5% of hyperdispersant, 0.01-10% of low-melting-point lubricating flame retardant auxiliary and 0.01-5% of organic sulfur-containing compound.
The piperazine phosphate is the prior art, and can be one or a mixture of more of piperazine monophosphate, piperazine diphosphate, piperazine pyrophosphate and piperazine polyphosphate which are not subjected to surface treatment or are subjected to surface treatment modification. Each of the above materials is not described in detail herein, and is known in the art, such as CN201310645585.8, entitled piperazine phosphate preparation method, which discloses a method for preparing piperazine diphosphate. Piperazine pyrophosphate is formed by the reaction of piperazine and phosphoric acid, piperazine is taken as a raw material, and piperazine pyrophosphate is obtained by the reaction of piperazine and phosphoric acid, distillation dehydration, centrifugation, washing, drying and crushing.
By the above-described method, a piperazine pyrophosphate, which is a prior art flame retardant, can be obtained, and will not be described in detail here. The surface-modified piperazine phosphate may be selected from the group consisting of surface-coated piperazine phosphate with epoxy, UV-cured polyacrylate, melamine, silane, titanate, or aluminate. The piperazine phosphate as a strong polar compound is easy to absorb water, has secondary agglomeration, and further can influence the processability of the flame retardant powder and the dispersion and compatibility in resin. These problems still remain with the non-surface treated piperazine phosphate, which, when mixed with the hyperdispersant, can significantly inhibit agglomeration of the powder, but still have some hygroscopicity. The piperazine phosphate after surface treatment can improve the water resistance of the powder, reduce agglomeration, and have better fluidity and dispersibility in resin after being mixed with a hyperdispersant. Therefore, it is preferable that the piperazine phosphate is a surface-treated piperazine phosphate.
The melamine and the derivatives thereof are the prior art, such as the application of melamine and the derivatives thereof disclosed in the 5 th and 6 th volumes of 2007 of chemical propellants and high molecular materials, and the specific content of the melamine and the derivatives thereof is disclosed. The melamine and the derivative thereof can be one or a mixture of a plurality of melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate and melamine cyanurate. However, the use of melamine and its derivatives in flame retardants is a prior art and therefore their function and mechanism of action are not described in detail.
The metal salt flame retardant synergist can be one or more of zinc oxide, zinc borate, silicon dioxide, titanium dioxide, aluminum oxide, aluminum hypophosphite, diethyl aluminum hypophosphite, dimethyl aluminum hypophosphite, diphenyl aluminum hypophosphite, magnesium silicate, aluminosilicate ester, zinc hypophosphite, zinc stannate, zinc sulfide, dimethyl zinc hypophosphite, diethyl zinc hypophosphite and diphenyl zinc hypophosphite. The use of the metal salt flame retardant synergist in flame retardants is also a prior art, and the function and mechanism of action thereof are not described in detail.
The hyperdispersant can be selected from a strong-polarity polyether hyperdispersant, or a medium-polarity polyester hyperdispersant which takes tertiary amine and a cyclic structure as anchoring groups, a series of carbamate groups or chain segments are uniformly distributed on a molecular chain or a grafted side chain, or a mixture of one or more of medium-polarity grafted acrylic hyperdispersants with free carboxylic acid and sulfonic acid hydrophilic groups. Because the piperazine phosphate has higher polarity, and is easy to absorb water and agglomerate. Therefore, according to the similar compatibility principle, the hyper-dispersant with certain polarity is selected to be favorable for dispersing the piperazine phosphate. The hyperdispersant replaces hydrophilic and lipophilic groups of traditional dispersants such as surfactants and the like with anchoring groups and solvated chains, and is tightly adsorbed on the surfaces of solid particles through the interactions such as ionic bonds, hydrogen bonds, covalent bonds, van der Waals forces and the like, so that mutual agglomeration among the particles is hindered, the bridging problem in the process of processing and blanking is avoided, and meanwhile, the dispersibility of the flame retardant in resin and the smoothness of the surfaces of products are improved.
The low melting point lubricating flame retardant aid may be selected from the group consisting of liquid phosphates such as t-butyl triphenyl phosphate, tetraphenyl bisphenol a diphosphate, tetraphenyl resorcinol diphosphate, and phenyl phosphate in a conventional manner having a certain flame retardant effect. The low melting point lubricating flame retardant aid may also be selected from solid flame retardant aids having a melting point below 200 ℃, such as one or a mixture of (6H) -dibenzo- (c, e) (1, 2) -phosphinohexane-6-one (DOPO), [ (6-oxy- (6H) -dibenzo- (c, e) (1, 2) -phosphinohexane-6-one) methyl ] -succinic acid (DOPO-ita), 10- (1, 4-butanedioic acid-2-yl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-1-oxide (DOPO-MA), 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10- -phenanthrene-10-oxide (ODOPB) hexaphenoxy cyclotriphosphazene, o-phenylenediamine cyclotriphosphazene, tris (epoxypropyl) isocyanurate in hexa-6H) -diphosphine esters. For solid flame retardant aids having a melting point below 200 ℃, the DOPO and phosphazene derivatives described above are preferred, but are not limited to the specific derivatives listed above. DOPO and phosphazene derivatives which are melted into liquid state in the processing process and have a melting point lower than 200 ℃ can be used as the low-melting-point lubricating flame retardant auxiliary agent.
The low-melting-point lubricating flame retardant auxiliary agents such as the phosphate, DOPO and phosphazene derivatives have certain flame retardance, so that the flame retardant efficiency of the flame retardant system can be enhanced. Meanwhile, the liquid phosphate flame retardant directly presents a liquid state in the processing process of double-screw extrusion granulation, so that the fluidity of the molten resin is improved, the melt index is increased, the dispersibility and compatibility of the flame retardant powder in the resin are further improved, the shearing action of the screw is reduced, the extrusion resistance is weakened, and the processing performance is remarkably improved. The melting point of DOPO and phosphazene derivatives is generally within 200 ℃, and the decomposition temperature is higher, and the processing temperature of the flame-retardant resin composition is generally 180-280 ℃, so that the DOPO and phosphazene derivatives are melted to be liquid, further the extrusion resistance is reduced, and the processing performance is improved. Therefore, DOPO and phosphazene derivatives with proper melting points can be selected for different resin systems and processing temperatures, so that the DOPO and phosphazene derivatives can be melted into liquid state in the double-screw extrusion processing process, the melt index is increased, and the processing performance is improved. Among them, DOPO and its derivatives have relatively better effects of improving flame retardance and processability.
The organic sulfur-containing compound may be a divalent sulfur-containing organic compound and a high-valence (tetravalent or hexavalent) sulfur-containing organic compound, which may be selected from one or a mixture of several of n-dodecyl sulfide, 4 '-dihydroxydiphenyl sulfide, 4' -sulfonyldiphenol, alkyl phenol disulfide, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, diphenyl sulfone.
Compared with the prior art, the piperazine phosphate compound flame retardant can inhibit secondary agglomeration under the action of the hyperdispersant, improve the fluidity of powder, and is matched with DOPO and phosphazene derivatives which have low melting point and easy melting and flame retardant effect as lubricants, and simultaneously organic sulfur-containing compounds as complementary acid sources to exert the synergistic effect of phosphorus and sulfur, promote condensed phase flame retardance to form carbon during combustion, further improve the flame retardance of a flame retardant system, and simultaneously, the compatibility of the organic sulfur-containing compounds and resin is better, and the influence on the mechanical properties of materials is smaller.
The flame-retardant resin composition consists of the compound halogen-free flame retardant and resin. The mass percentage of the halogen-free flame retardant in the resin composition is 15-50%. The flame-retardant resin composition is pelletized by a twin-screw extruder at 180-280 ℃ to form resin composition granules capable of being used for manufacturing various products.
The resin for flame retarding of the halogen-free flame retardant can be homo-and co-polymerized polypropylene, glass fiber reinforced polypropylene, continuous long glass fiber reinforced polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, thermoplastic elastomer, silicone rubber and ethylene propylene diene monomer, preferably polypropylene and glass fiber reinforced system thereof. The processing temperatures of different resin materials have certain difference, the processing temperature of the conventional polypropylene and glass fiber reinforced materials is generally 180-210 ℃, and the processing temperature of the continuous long glass fiber reinforced polypropylene is 220-280 ℃. The selection of each component, especially the low-melting-point lubricating flame retardant auxiliary agent, in the invention is determined by screening according to the change of the processing temperature of the resin.
Meanwhile, the flame-retardant resin composition is not limited to the use of the components, and according to different requirements of the application environment of the flame-retardant resin, antioxidants, ultraviolet-resistant agents, anti-dripping agents, antistatic agents, fillers, lubricants, coupling agents, compatilizers and the like which are commonly used in modified plastic systems can be added, wherein the use amount of each component is conventional and is selected from the existing commercial products.
Compared with the prior art, the halogen-free flame retardant provided by the invention has the advantages that the piperazine phosphate, the melamine and the derivatives thereof, the metal salt flame retardant synergist, the hyperdispersant, the low-melting-point lubricating flame retardant auxiliary agent and the organic sulfur-containing compound are added, different elements play different roles in the flame retardant, specifically, the piperazine phosphate compounded halogen-free flame retardant mainly plays a flame retardant role through a condensed phase, and the acid source, the carbon source and the air source cooperate, so that an expanded carbon layer is formed on the surface of the material to insulate heat and insulate oxygen to inhibit molten drops, and further the combustion is interrupted. After the low-melting-point lubricating flame-retardant auxiliary agent is added, the melt index of the resin can be increased, molten dripping is easy to generate during combustion, and the auxiliary agent with the anti-dripping effect is required to be matched. The sulfur element in the organic sulfur-containing compound can change the decomposition process of the polymer, and can be used as a complementary acid source to generate better flame-retardant synergistic effect with phosphorus and nitrogen elements in flame retardants, phosphate esters, DOPO, phosphazenes and other lubricating processing aids, so that sulfuric acid substances are released by thermal decomposition during combustion, and the generated acid and carbon source are combined to generate esterification reaction, so that the flame-retardant char formation of a condensed phase is promoted, the quality and the continuity of a char layer are improved, and secondary combustion caused by molten drops is prevented. Meanwhile, the organic sulfur-containing compound has good compatibility with the resin material, and the influence of the halogen-free flame retardant on the mechanical property of the material is reduced. Meanwhile, the invention has the following advantages:
(1) Aiming at the problems that piperazine phosphate compound flame retardant is easy to absorb moisture and agglomerate and is easy to process and bridge, hyper-dispersants with similar polarities are selected to isolate flame retardant powder, so that secondary agglomeration of the powder is effectively inhibited, the particle size of the halogen-free flame retardant is reduced, and the powder characteristics and the dispersibility in resin can be improved.
(2) Liquid phosphate or DOPO, phosphazene derivatives and other low-melting-point auxiliary agents with certain flame retardant function are added, and the liquid phosphate or DOPO, phosphazene derivatives and other low-melting-point auxiliary agents can be quickly melted in the processing process, so that the melt flow rate of resin in the flame retardant resin composition can be increased, the shearing force of a screw and the processing resistance can be reduced, the degradation of the flame retardant caused by shearing heat can be avoided, the processing tolerance and the production efficiency are improved, and meanwhile, the dispersibility and the compatibility of the flame retardant powder in the resin are improved.
(3) The organic sulfur-containing compound is used as a supplementary acid source, so that the condensed phase can be promoted to form carbon, the quality and the continuity of an expanded carbon layer are improved, and further, combustion molten drops can be effectively inhibited, and the secondary ignition of a fire disaster is prevented.
(4) The flame retardant disclosed by the invention has higher thermal decomposition temperature, is suitable for systems with higher processing temperatures such as continuous long glass fiber reinforced polypropylene and the like and injection molding processes, and has the advantages of smooth surface of a flame retardant finished piece, no white spots and high yield.
In the following embodiments or examples, unless otherwise specified, the raw material components used are commercial products purchased from the market by those skilled in the art or products prepared by a known method.
The sample testing method and criteria are as follows:
1) Melt flow index (MF I): measured according to GB/T3682.1 standard.
2) Surface smoothness: the surface smoothness of the extruded bars was manually evaluated, o indicated that the surface smoothness of the bars was good, Δ indicated that the surface smoothness of the bars was general, and x indicated that the surface smoothness of the bars was poor.
3) Vertical combustion progression: tested according to GB/T2408 standard.
According to the mass ratio of each component in the table 1, the piperazine phosphate, the melamine and the derivatives thereof, the metal salt flame retardant synergist, the hyperdispersant, the low-melting-point lubricating flame retardant auxiliary agent and the organic sulfur-containing compound are added into a high-speed mixer according to the mass ratio of each component in the table 1, and are mixed for 10min to obtain the compound flame retardant mixture. The polypropylene resin and the compound flame retardant are premixed in a low-speed mixer in proportion for 8 min, extruded in a double-screw extruder through a main feeding port, and water-cooled and pelletized at 180-200 ℃ in each area of the extruder.
Table 1 formulation of comparative example 1 and examples 1-9 flame retardant polypropylene materials
Table 2 results of Performance test of flame retardant Polypropylene materials of comparative example 1 and examples 1-9
Under the same extrusion process conditions, the phenomena of powder bridging, uneven blanking and broken extrusion of the comparative example 1 sometimes occur, technicians are required to observe the blanking condition in a blanking hopper at intervals, the labor intensity of the personnel is increased, the production efficiency is reduced, and the surface of a spline is rough and has white spots visible to naked eyes. In the examples 1-9, after the hyperdispersant, the low-melting-point lubricating flame retardant auxiliary agent and the organic sulfur-containing compound are added into the piperazine phosphate compound flame retardant, the conditions are not generated in the processing process, the blanking is uniform, the strips are continuous, and the surface of the spline is smooth and has no white spots.
From the test results of the flame-retardant polypropylene materials of comparative example 1 and example 1 in table 2, it can be seen that after the hyperdispersant, the low-melting-point lubricating flame retardant auxiliary agent and the organic sulfur-containing compound are added, the flow rate of the flame retardant powder is increased, the melt flow rate of the polypropylene resin is increased, the surface smoothness is good, the flame retardant property is slightly improved, and the mechanical property is obviously improved. The formulations of examples 1 and 2 compare formulation data before and after surface modification of piperazine pyrophosphate, and the epoxy resin treated piperazine pyrophosphate has relatively better properties of the flame retardant powder and the flame retardant resin, reduced water solubility of the powder and is not easy to agglomerate after long-term storage.
The comparative examples 2 to 7 in Table 3 show the effects on the processing and performance of the compounded flame retardant powder and flame retardant polypropylene materials without using one or two of hyperdispersant, low melting point lubricating flame retardant aid, and organic sulfur compound, and the specific formulation and test results are shown in tables 3 and 4.
Table 3 specific formulations of comparative examples 2-7
Table 4 results of Performance test of comparative examples 2 to 7
| Melt index (g/10 min,230 ℃,2.16 kg) | 3.76 | 2.81 | 3.65 | 2.79 | 3.62 | 2.24 |
| Surface smoothness | × | × | ○ | × | × | × |
| UL94(1.6mm) | V-0 | V-0 | V-1 | V-2 | V-1 | V-0 |
Comparison of the performance test data of comparative examples 2-7 in Table 4 and example 1 in Table 1 shows that the performance of the flame retardant polypropylene exhibited a corresponding variation without the addition of hyperdispersant, low melting point lubricating flame retardant aid, organic sulfur containing compound. When no hyperdispersant was added, the surface smoothness of the bars was poor, and white spots were exhibited to varying degrees. When the low-melting lubricating flame retardant auxiliary is not added, the melt flow rate of the flame retardant resin is reduced, the surface smoothness of the spline is deteriorated, and the processability is lowered. When no sulfur-containing compound is added, the flame retardant rating of the flame retardant polypropylene is reduced, the combustion is overtime or there are droplets. The influence of the addition of the auxiliary agent on the performance of the flame-retardant material is avoided, the flame-retardant material is matched with the starting point of the screening of the auxiliary agent by the inventor and the functions exerted in the whole formula, and further different effects exerted by the auxiliary agents in the formula are verified, so that the flame-retardant material is an indispensable component in the flame-retardant formula.
From the cost and performance of the flame-retardant product, adding inorganic filler and glass fiber reinforced material into polypropylene resin is a commonly used method in the industries of automobiles, household appliances and the like. Comparative example 8 and examples 10-11 compare the performance of flame retardant polypropylene materials at different talc loadings, comparative example 9 and examples 12-14 compare the performance of glass fiber reinforced flame retardant polypropylene at different levels, and specific formulations and test data are shown in tables 5 and 6.
Table 5 specific formulations for comparative examples 8 and 9 and examples 10-14
Table 6 results of Performance test of comparative examples 8 and 9 and examples 10 to 14
| Melt index (g/10 min,230 ℃,2.16 kg) | 1.23 | 0.84 | 3.05 | 2.79 | 2.48 | 1.76 | 1.34 |
| Surface smoothness | △ | × | ○ | ○ | ○ | ○ | ○ |
| UL94(1.6mm) | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
From the test data of table 6, comparing the flame retardant materials of talcum powder and glass fiber reinforced polypropylene, it is found that when only flame retardant and filler are added, the melt fluidity of the flame retardant materials is remarkably reduced, and the surface smoothness of the sample bar is poor; when a small amount of hyperdispersant, DOPO and organic sulfur-containing compound are added, the flame retardant grade of the flame retardant material is not changed, but the melt flow rate is obviously increased, and the surface smoothness of the sample is better.
The above is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalent substitutions or improvements within the spirit of the present invention are intended to be covered by the claims of the present invention.
Claims (8)
1. The halogen-free flame retardant with good flame retardance and processability is characterized by comprising, by mass, 40-80% of piperazine phosphate, 20-50% of melamine and derivatives thereof, 1-10% of metal salt flame retardant synergist, 0.01-5% of hyperdispersant, 0.01-10% of low-melting lubricating flame retardant aid and 0.01-5% of organic sulfur-containing compound, wherein the low-melting lubricating flame retardant aid is liquid organic phosphate or solid with a melting point lower than 200 ℃ in a conventional state.
2. The halogen-free flame retardant with good flame retardance and processability as set forth in claim 1, wherein the piperazine phosphate is one or a mixture of more of piperazine monophosphate, piperazine diphosphate, piperazine pyrophosphate and piperazine polyphosphate which is not surface-treated or surface-treated.
3. The halogen-free flame retardant with good flame retardance and processability as set forth in claim 1, wherein said melamine and its derivatives are one or a mixture of more of melamine, melamine phosphate, melamine pyrophosphate, melamine polyphosphate and melamine cyanurate.
4. The halogen-free flame retardant with good flame retardance and processability as set forth in claim 1, wherein the metal salt flame retardant synergist is one or a mixture of several of zinc oxide, zinc borate, silicon dioxide, titanium dioxide, aluminum oxide, aluminum hypophosphite, aluminum dimethyl hypophosphite, aluminum diphenyl hypophosphite, magnesium silicate, aluminosilicate, zinc hypophosphite, zinc stannate, zinc sulfide, zinc dimethyl hypophosphite, zinc diethyl hypophosphite and zinc diphenyl hypophosphite.
5. The halogen-free flame retardant with good flame retardance and processability of claim 1, wherein the hyperdispersant is one or a mixture of more of polyether hyperdispersant, polyester hyperdispersant and polyacrylate hyperdispersant.
6. A halogen-free flame retardant with good flame retardance and processability as claimed in claim 1, wherein the low melting lubricating flame retardant auxiliary is (6H) -dibenzo- (c, e) (1, 2) -phosphinothioyl-6-one (DOPO), [ (6-oxo- (6H) -dibenzo- (c, e) (1, 2) -phosphinothioyl-6-one) methyl ] -succinic acid (DOPO-ITA), 10- (1, 4-butanedioic acid-2-yl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-1-oxide (DOPO-MA), 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10- -phenanthrene-10-oxide (ODOPB) and/or hexaphenoxy cyclotriphosphazene, o-phenylenediamine cyclotriphosphazene and/or t-butyl triphenyl phosphate, tetraphenyl bisphenol A diphosphate, tetraphenyl diphosphate, epoxy phosphate and/or a mixture of one or more of cyanuric acid phosphates.
7. The halogen-free flame retardant with good flame retardance and processability as set forth in claim 1, wherein the organic sulfur-containing compound is selected from one or a mixture of more of n-dodecyl sulfide, 4 '-dihydroxydiphenyl sulfide, 4' -sulfonyldiphenol, alkylphenol disulfide, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and diphenylsulfone.
8. A flame-retardant resin composition characterized in that: the flame-retardant resin composition consists of the halogen-free flame retardant with good flame retardance and processability and resin according to any one of claims 1 to 7, wherein the mass percentage of the halogen-free flame retardant with good flame retardance and processability is 15-50%, and the halogen-free flame retardant and the resin are pelletized by a double screw extruder to prepare the flame-retardant resin composition, and the temperature of the extruder is 180-280 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011350705.8A CN112409693B (en) | 2020-11-26 | 2020-11-26 | Halogen-free flame retardant with good flame retardance and processability and flame-retardant resin composition |
| PCT/CN2020/137511 WO2022110392A1 (en) | 2020-11-26 | 2020-12-18 | Halogen-free flame retardant having good flame retardancy and processibility, and flame-retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011350705.8A CN112409693B (en) | 2020-11-26 | 2020-11-26 | Halogen-free flame retardant with good flame retardance and processability and flame-retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112409693A CN112409693A (en) | 2021-02-26 |
| CN112409693B true CN112409693B (en) | 2023-05-09 |
Family
ID=74843273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011350705.8A Active CN112409693B (en) | 2020-11-26 | 2020-11-26 | Halogen-free flame retardant with good flame retardance and processability and flame-retardant resin composition |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112409693B (en) |
| WO (1) | WO2022110392A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248793B (en) * | 2021-04-21 | 2022-10-14 | 国家能源集团宁夏煤业有限责任公司 | Halogen-free flame retardant-antistatic-stabilizer composition, halogen-free flame retardant-antistatic polyethylene composite material and preparation method thereof |
| CN115386142B (en) * | 2021-05-25 | 2023-07-11 | 金发科技股份有限公司 | Well-dispersed halogen-free flame retardant, and preparation method and application thereof |
| CN114031844B (en) * | 2021-10-25 | 2023-10-03 | 浙江旭森阻燃剂股份有限公司 | Halogen-free flame-retardant master batch for continuous long glass fiber reinforced polypropylene and preparation method thereof |
| CN114213807B (en) * | 2021-12-15 | 2023-06-27 | 天津大学 | High-thermal-stability intumescent flame retardant modified epoxy resin material and preparation method thereof |
| CN114539618B (en) * | 2022-02-15 | 2023-07-11 | 东莞市宏泰基阻燃材料有限公司 | Silicone rubber halogen-free flame retardant, and preparation method and application thereof |
| CN114773871B (en) * | 2022-03-31 | 2023-08-22 | 上海化工研究院有限公司 | High-stability and high-flame-retardance composite elastomer material and preparation method thereof |
| CN115536909B (en) * | 2022-06-17 | 2023-11-17 | 上海力道新材料科技股份有限公司 | Halogen-free flame retardant composition and preparation method and application thereof |
| CN115216090B (en) * | 2022-08-25 | 2023-07-07 | 佛山市湘聚新材料有限公司 | Building template material and preparation method thereof |
| CN115232404B (en) * | 2022-09-06 | 2023-06-06 | 金旸（厦门）新材料科技有限公司 | Precipitation-resistant high-apparent phosphorus-nitrogen flame-retardant polypropylene composite material and preparation method thereof |
| CN115772285A (en) * | 2022-12-12 | 2023-03-10 | 云南云天化股份有限公司 | Preparation method of modified piperazine pyrophosphate and modified piperazine pyrophosphate |
| CN116041846B (en) * | 2022-12-28 | 2024-02-23 | 上海日之升科技有限公司 | Low-creep ultraviolet flame-retardant material used in high-frequency vibration environment |
| CN116285013B (en) * | 2023-03-15 | 2024-05-03 | 赛得利(江苏)纤维有限公司 | Flame-retardant viscose production process |
| CN116656130B (en) * | 2023-06-06 | 2024-02-20 | 江西佳化新材料有限公司 | Self-compatibilizing flame-retardant organic silicon thermoplastic elastomer material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101765629A (en) * | 2007-07-28 | 2010-06-30 | 化学制造布敦海姆两合公司 | Halogen-free flame-proofing agent |
| WO2014060004A1 (en) * | 2012-10-16 | 2014-04-24 | Wolfgang Wehner | Method for producing metal-2-hydroxydiphenyl-2'-(thio)phosphinates and metal-diphenylene-(thio)phosphonates, compositions containing same and use thereof as flame-proofing agents |
| CN104854184A (en) * | 2013-12-10 | 2015-08-19 | Lg化学株式会社 | Polyolefin flame-retardant resin composition and molded article |
| CN110483898A (en) * | 2019-09-29 | 2019-11-22 | 上海化工研究院有限公司 | A kind of resistance to precipitation halogen-free flame retardants of high fluidity and its preparation method and application |
| CN110964256A (en) * | 2019-12-27 | 2020-04-07 | 重庆科聚孚工程塑料有限责任公司 | Efficient halogen-free intumescent flame-retardant glass fiber reinforced polypropylene material and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4753498B2 (en) * | 2001-07-17 | 2011-08-24 | 株式会社Ａｄｅｋａ | Flame retardant synthetic resin composition |
| CN104059278A (en) * | 2014-06-30 | 2014-09-24 | 成都硕屋科技有限公司 | Hydrolysis-resistant migration-free halogen-free flame-retardant polyolefin composition and preparation method thereof |
| WO2016125612A1 (en) * | 2015-02-06 | 2016-08-11 | 株式会社Adeka | Flame-retardant composition and flame-retardant synthetic resin composition |
| US10266673B2 (en) * | 2015-02-06 | 2019-04-23 | Adeka Corporation | Flame-retardant polypropylene composition |
| WO2017159161A1 (en) * | 2016-03-14 | 2017-09-21 | 株式会社Adeka | Flame retardant thermoplastic polyurethane resin composition |
| EP3680310A4 (en) * | 2017-09-07 | 2021-05-12 | Adeka Corporation | Composition, and flame-retardant resin composition |
| CN110591299A (en) * | 2019-09-30 | 2019-12-20 | 上海化工研究院有限公司 | Halogen-free flame-retardant cable material for new energy automobile charging cable and preparation method |
-
2020
- 2020-11-26 CN CN202011350705.8A patent/CN112409693B/en active Active
- 2020-12-18 WO PCT/CN2020/137511 patent/WO2022110392A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101765629A (en) * | 2007-07-28 | 2010-06-30 | 化学制造布敦海姆两合公司 | Halogen-free flame-proofing agent |
| WO2014060004A1 (en) * | 2012-10-16 | 2014-04-24 | Wolfgang Wehner | Method for producing metal-2-hydroxydiphenyl-2'-(thio)phosphinates and metal-diphenylene-(thio)phosphonates, compositions containing same and use thereof as flame-proofing agents |
| CN104854184A (en) * | 2013-12-10 | 2015-08-19 | Lg化学株式会社 | Polyolefin flame-retardant resin composition and molded article |
| CN110483898A (en) * | 2019-09-29 | 2019-11-22 | 上海化工研究院有限公司 | A kind of resistance to precipitation halogen-free flame retardants of high fluidity and its preparation method and application |
| CN110964256A (en) * | 2019-12-27 | 2020-04-07 | 重庆科聚孚工程塑料有限责任公司 | Efficient halogen-free intumescent flame-retardant glass fiber reinforced polypropylene material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 曾倩等.一种磷-氮系阻燃剂的制备及其性能.《工程塑料应用》.2020,第48卷(2),114-118. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112409693A (en) | 2021-02-26 |
| WO2022110392A1 (en) | 2022-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112409693B (en) | Halogen-free flame retardant with good flame retardance and processability and flame-retardant resin composition | |
| CN109233101B (en) | Heat-resistant flame-retardant polypropylene composition and preparation method thereof | |
| KR101322145B1 (en) | Thermoplastic halogen-free flame retardant ABS resin composition | |
| CN109135046B (en) | Flame-retardant polyolefin composition and preparation method thereof | |
| CN111333960A (en) | Antimony-free flame-retardant polypropylene composition and preparation method thereof | |
| CN109206829B (en) | High-yellowing-resistance precipitation-resistance halogen-free flame-retardant thermoplastic elastomer composition and preparation method thereof | |
| CN109135048B (en) | Flame-retardant polyolefin composition and preparation method thereof | |
| US7462662B2 (en) | Fire-retarded polycarbonate resin composition | |
| CN108976595B (en) | Flame-retardant polyolefin composition and preparation method thereof | |
| EP3140346B1 (en) | Environmental friendly flame retardant moulding compositions based on thermoplastic impact modified styrenic polymers | |
| CN104693760A (en) | Blended alloy of polycarbonate and polybutylene terephthalate | |
| CN103709666A (en) | Halogen-free and flame retardation modified PET engineering plastic and preparation method thereof | |
| CN113462140B (en) | Flame-retardant polycarbonate composite material and preparation method thereof | |
| KR20070091037A (en) | Fire-retardant composition | |
| KR20150067863A (en) | Polypropylene flame retardant resin composition and extrusion tubing molded product | |
| CN112080074B (en) | Flame-retardant polypropylene composition and preparation method and application thereof | |
| CN108976593B (en) | Flame-retardant polyolefin composition and preparation method thereof | |
| CN111748156A (en) | Halogen-free flame-retardant mineral powder reinforced polypropylene composition | |
| JP7153029B2 (en) | Flame-retardant styrene-containing composition | |
| DE112017003897T5 (en) | Flame retardant polyester composition | |
| KR20130130320A (en) | Eco-friendly polyester flame retarding resin composition without any halogen-antimony | |
| WO2012011519A1 (en) | Fire retarding agent containing cyclic amine salt, and fire-retardant resin composition | |
| CN111205555A (en) | Polypropylene flame-retardant composite material containing 'three-in-one' flame retardant and preparation method thereof | |
| JP6924823B2 (en) | Flame-retardant transparent polycarbonate composition | |
| WO2020067205A1 (en) | Flame-retardant resin composition and molded object |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 166 Chenggong Road, Huimin street, Jiashan County, Jiaxing City, Zhejiang Province Applicant after: Zhejiang xusen flame retardant Co.,Ltd. Address before: 166 Chenggong Road, Huimin street, Jiashan County, Jiaxing City, Zhejiang Province Applicant before: ZHEJIANG XUSEN HALOGEN FREE SMOKE ABATEMENT FIRE RETARDANT CO.,LTD. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |